Process for preparing valuable compounds from the refining wastes of cracked products, particularly cracked benzines



Patented July 26, 1932 curl-En STATES PATENT? OFFICE WACLAW VON PIOTROWSKI AND J'CZEF WINKLER, OF DROHOBYCZ, POLAND, ASSIGNOBS TO- GALICYJ'SKIE TOWABZSTWO NAFTOWE GALIC-TA S. A., OF DROHOBYCZ, POLAHD,

a comm-non or mm) PROCESS FOB' PREPARING- VALUABLE COMPOUND FROM THE EEFINING WASTES OI CRACKED PRODUCTS, PARTICULARLY CRACKED BENZINES Io Drawing. Application filed October 29, 1928, Serial No. 315,911, and in Poland September 24, 1927.

This invention relates to a process for obtaining, from the acids and lyes obtained as waste products in the refining processes of cracked products, particularly cracked benzines, various valuable compounds, some of to or slightly alkaline liquids. A supernatant oily layer and a lower aqueous layer are formed thereby. The oily layer contains the compounds of olefine character, whilst the main portion of the alcohols are to be found in the aqueous layer. The alcohol residues, which remain in the oily layer are removed therefrom by washing with water and the washings added to the first aqueous layer. The latter is then neutralized and subjected to steam distillation whereby a water-alcohol mixture comes'over, which is fractionated and distilled in lmown manner to effect a further separation of the constituents. The alcohols obtained in thisway may be employed for denaturing and other purposes, for which higher alcohols are used.

The washed oily layer is also neutralized, again washed and then distilled with steam. The residue left in the still is separately further worked up. The distillate consists of a mixture of unsaturated compounds, which can be converted in known manner by condensation into compounds of higher molecular wei'ht or transformed with siccatives into easi y drying oils of a rubber-like character. Both the distillation and residual products are particularly adapted to be employed in the manufacture of lacquer and.

. in at this temperature.

varnish.

The following example illustrates how the process of this invention can be carriedinto effect:-

The benzine obtained for example, ina Cross plant is refined with 3% of about M separates out as an upper layer from the aqueous liquid underneath.

The acid-refined benzine is next washed with caustic lye of 4 B. The waste liquor from this operation is employed for neutral-' izing the waste acid.

The two layers formed from the acid tar are further worked up as follows (a) Further treatment of aqueous layer.

his layer composed of dilute sulphuric acid and alcohols is distilled with superheated steam. A distillate coming over between C. and 150 C. is collected. This water-alcohol distillate is rectified in known manner in a column apparatus. The yield in alcohols (butyl, amyl, hexyl alcohol etc.) amounts to about 25% of the acid tar treated and depends, (1) on the composition of the crude benzinethe greater the content of lower boiling constituents (of about 50 C.,60C.),

the higher is the yield in alcohols; (2) on the concentration of the sulphuric acid employed for the refining process and (3) on the refining temperature. The higher the refining temperature and the greater the acid concentration the lower is the yield inv alcohol.

(6) Further treatment of the oily layer. The oily layer is neutralized, dehydrated and distilled over lime. Steam is then passed The fractions coming over between 50 C..and 200 C. are collected together and form the first fraction (fraction 1), the second fraction (fraction 2) consists of the oils distilling off at between 200 C. and 280 C. When noth- .ing more distils over at this temperature the steam is turned off, the content of the still allowed to cool to about 140 C. and air blown more or less consistent asphalt-like products are obtained. These products are distinguished by their high elasticity and, unlike the known asphalts, are soluble in benzine and can, therefore, be employed as lacquers. Fraction 1 is refined with lye and sodium plumbite and again rectified. The product forms a useful insecticide.

Fraction 2 is boiled with a siccativc (for example manganese or cobalt siccative) when,

' and sodium plumbite,

according to the temperature, duration of boiling, nature and quantity of siccative, varnish-like products are obtained. 45% of manganese siccative is, for example, added to fraction 2 and the mixture boiled for about 24 hours at a temperature of about 180 C.

What we claim is 1. A method of producin an insecticide from the waste sludge of crac ed mineral oils which comprises mixing the waste acid-containing sludge with water and a weak alkaline solution, allowing the mixture to separate into two layers, removing the upper layer, subjecting the same to steam distillation, thereby producing a plurality of fractions collecting the fractions coming over between C. and 200 (lcond'ensing and combining the fractions to form a condensate and refining the condensate by treating it with lye and sodium plumbite and finally rectifying the refined condensate, thereby producing the insecticide.

2. A method .of producing an insecticide from the waste sludge of cracked benzine which comprises mixing the waste acid-containing sludge with water and a waste lye, ale

lowing the mixture to separate into two layers, removing the'upper layer, subjecting the same to steam distillation, thereby producing a plurality of fractions, collecting the fractions coming over between 50 C. and 200 C. and condensing to form a condensate, and refining the condensate by treating it with lye and finally rectifying the refined condensate, thereby producing the insecticide.

3. A process for obtaining valuable compounds as insecticides, denaturizing substances, and odorizing agents from waste acids of the mineral oil refining industry, said waste acids having been previously ob- 200 and 280 C. after condensing the latter, to form a final condensate comprising the desired valuable compounds.

4. A process for obtaining valuable compounds as insecticides, denaturizing substances, and odorizing agents from waste acids of the mineral oil refining industry, said waste acids having been prevlously obtained through known processes, the present process consisting in distilling with steam the oily layer formed upon neutralization of the sludge acids in the recovery of the acid sludge from the refining of benzine, ing a plurality of fractions coming over between 50 and 280 C. segregating those fractions distilling over between 50 and 200 (3., and refining them in the form of a condensate with sodium plumbite, then rectifying the said condensate, and finally combining the rectified condensate with the remaining fractions, coming over between 200 and 280 C. after condensing the latter, to form a final condensate comprising the desired valuable compound.

In testimony whereof we afiixour slgnatu e r S WACLAW VON PIOTROWSKI.

JOZEF WINKLEB.

thereby productained through known recesses, the present I process consisting in istilling with steam the oily layer formed upon distillation and subsequent neutralization of the acids with water and alkali in the recovery of the acid sludge from the refining of cracked benzine, thereby producing a plurality of fractions coming over between 50 and 280 0., segregating those fractions distilling over between 50 and 200 C. and refining them in the form of a condensate with sodium plumbite, then rectifying the said condensate, and finally combining the rectified condensate. with the remaining fractions, coming over between 

